Alkoxylated polymers

ABSTRACT

The present invention provides alkoxylated polymers. The alkoxylated polymers have two or more alkoxylated sites. The alkoxylated polymers can comprise any monomers and/or oligomers that contain one or more functional groups with an active hydrogen. The alkoxylated polymers are useful in any application for which polymers are generally used. For example, the alkoxylated polymers are useful as additives in ink and coating compositions.

The present application claims priority to U.S. Provisional ApplicationNos. 62/002,300 and 62/006,948, filed May 23, 2014 and Jun. 3, 2014respectively, which are hereby incorporated herein in their entirety.

FIELD OF THE INVENTION

The present invention is in the field of polymers and polymerdevelopment. Described herein are alkoxylated polymers.

BACKGROUND

Today, the use of polymers is ubiquitous. As polymers have beendeveloped and improved, their versatility has increased. For example,everyday items such as food packaging (e.g. bags and bottles),adhesives, protective films, optical elements, flexible foams, paints,varnishes, printing inks and coatings, as well as may others, employpolymers in some way. Polymers may be used as a binder in a composition,forming a solid film or structure. Polymers may also be used asadditives in, for example, paints, inks, and coatings. When used asadditives, they be used as dispersants for other components of acomposition, or as diluents to increase solubility of other componentsin a composition.

For example, polymers are used in several ways in printing ink andcoating compositions. Many printers seek to increase their productivityby employing high speed printing. However, as printing speed increases,there is a greater tendency for printing defects. Moreover, because ofthe constraints placed upon ink formulations suitable for high speedprinting, other properties, such as opacity, gloss, scratch resistance,and laydown of the ink are often compromised.

Because high speed printing inks and coatings must have a low viscosity,the amount of solids in a formulation must often be reduced. However, ifthe amount of solids in an ink or coating is limited, it is difficult toload enough colorant to achieve the desired opacity and gloss. Thus,there is often a compromise between the desired opacity and gloss, andthe maximum printing speed.

Gloss is affected by the smoothness of a printed ink or coating. A roughcoating will reflect less light, and therefore gloss will be reduced.Therefore, it is important that the laydown of an ink or coating is suchthat a smooth printed surface is formed.

Properties related to the durability of the ink or coating, such asscratch resistance, are also impacted by the constraints of high speedprinting formulations. Binders and resins that have a low enoughviscosity to be printed at high speed often produce tacky, soft printedsurfaces. The tacky, soft printed surfaces are not durable, andproperties such as scratch resistance are compromised.

Thus, the ideal ink or coating for high speed printing would haveseemingly incompatible characteristics. A high speed printing ink orcoating must have a low viscosity. But, it is often desired to achievehigh opacity, which requires a higher solids loading (i.e. colorant),which leads to higher viscosity. Although durable coatings are desired,binders and resins that have a low viscosity suitable for high speedprinting are often not durable.

Coating and ink compositions (such as varnishes, paints, and printinginks) are colored by the incorporation of dyes or pigments. While dyesare generally soluble, pigments are not. Therefore, to achieve goodcolor intensity, gloss, hiding power, lightfastness, weather resistanceetc. when pigments are used, the pigment particles must be homogeneouslymixed into the composition.

To achieve a homogeneous mixture, pigments are dispersed in the liquidcoating composition. Stable dispersion of a pigment entails three steps:wetting of the pigment particles (or aggregates or agglomerates ofpigment particles) by the coating (generally resin) solution; dispersionof the pigment particles into the liquid (through mechanical energy);and stabilization. Dispersing agents can be used to achieve the firstand third steps.

During wetting, the resin solution replaces the air between the pigmentparticles, aggregates, and/or agglomerates. Aggregates are groups ofprimary pigment particles connected at their face through intermolecularforces. Agglomerates are similar to aggregation, but are groups ofprimary particles connected at their edges and corners through weakerattractions to each other than aggregates. To achieve wetting of thepigment particles, a dispersing agent (also known as a surfactant) canbe added to the composition to modify the surface tension of the liquidand the interfacial tension between the liquid and the pigmentparticles.

During the second, dispersing step, mechanical force, in the form ofimpact and shear forces, is applied to the composition. This can be doneby mixing with, for example, a bead mill or a roll mill. This breaks upthe pigment agglomerates into smaller units, which are uniformlydistributed (i.e. dispersed) into the liquid composition. However,without the third step, stabilization, the pigment particles tend toregroup, or flocculate, and the pigment would no longer be dispersed.

Addition of dispersing agents to the liquid composition stabilizes thepigment particles, and prevents them from flocculating. One family ofdispersing agents is polymeric dispersants. Polymeric dispersantsstabilize the dispersion by “steric stabilization.” One part of apolymeric dispersant, the anchoring group, adsorbs onto the pigmentparticles. The other part, the polymeric chain, is soluble in the liquidcomposition, and extends into the liquid composition. A layer is formedaround the pigment particles, effectively keeping them separated, andpreventing flocculation. The pigment particles thus remain evenlydispersed in the liquid composition.

WO 2010/149962 teaches the use of a styrenic branched addition copolymeras a dispersant in a gaseous, liquid or solid formulation wherein thecopolymer is obtainable by addition polymerization. These copolymers canbe used as dispersants for pigments; or as dispersants for inks, paints,sealants, tinters, powder coatings, and injection molding applications.

US 2010/0145001 relates to a branched, hybrid polymer obtained byaddition polymerization, preferably a free radical polymerizationprocess, comprising organic chains and inorganic chains. The copolymersmay be incorporated into compositions containing only a carrier ordiluent, or also comprising an active ingredient. The copolymers areparticularly suitable for use in laundry compositions, especially asagents to prevent transfer of dye back onto the fabric.

US 2011/0283908 is directed to high opacity polyurethane resins producedby the polymerization of polyisocyanates with polymeric polyols andsubsequent chain extension with polyamines. The resins are capable ofproviding high opacity printing inks when formulated with whitepigments.

Although a range of polymers have been developed for specific functions,polymers formulated to have wide ranging uses are more challenging. Forexample, with the increasing drive for productivity, there is a need toformulate inks and coatings that have high opacity and durability, whilehaving a low viscosity suitable for high speed applications, such ashigh speed printing. The choice of polymers used is critical toachieving these desired properties.

SUMMARY OF THE INVENTION

The present invention provides alkoxylated polymers. The alkoxylatedpolymers have two or more alkoxylated sites. The alkoxylated polymerscan comprise any monomers and/or oligomers that contain one or morefunctional groups with an active hydrogen.

In a particular aspect, the present invention provides an alkoxylatedpolymer comprising:

-   -   a) a backbone with one or more alkoxylated sites;    -   b) terminal ends each of which is a site that can be        alkoxylated; and    -   c) and one or more polyfunctional monomers or oligomers having        two or more functional polar groups with an active hydrogen, or        mixtures thereof.

The functional polar groups are preferably hydroxyl, carboxyl, thiol,amino, imino, amido, or ureido. Preferably, at least one of the monomersand/or oligomers is functionalized by one or more functional hydroxylgroups.

In a particular aspect, the present invention provides an alkoxylatedpolyester comprising:

-   -   a) a backbone with one or more alkoxylated sites;    -   b) terminal ends each of which is a site that can be        alkoxylated;    -   c) one or more di- or higher functional polyols; and    -   d) one or more diacids or anhydrides, or mixtures thereof.

In a particular aspect, the present invention provides an alkoxylatedpolyurethane comprising:

-   -   a) a backbone with one or more alkoxylated sites;    -   b) terminal ends each of which is a site that can be        alkoxylated;    -   c) one or more diisocyanates; and    -   d) one or more di- or higher functional polyols.

In a particular aspect, the present invention provides an alkoxylatedpolyacrylic comprising:

-   -   a) a backbone with one or more alkoxylated sites;    -   b) terminal ends each of which is a site that can be        alkoxylated;    -   c) one or more hydroxyl functional acrylic monomers, or carboxyl        functional acrylic monomers, or mixtures thereof;    -   d) one or more additional acrylic or styrenic monomers; and    -   e) one or more di- or higher functional polyols.

The alkoxylated polymers can be used for any purpose for which polymersare generally used, including, but not limited to, ink and coatingcompositions, packaging such as bags and bottles, electricalapplications such as insulators or conductors on circuit boards,adhesives, protective films, flexible foams, optical elements, etc.Preferably, the alkoxylated polymers are used as additives in ink andcoating compositions. Preferred are high speed printing inks. Thealkoxylated polymers may, for example, function as dispersants or as lowtack binders in the ink and coating compositions. Advantageously, thealkoxylation of the polymers renders them more compatible with otherpolymers and resins typically found in ink and coating compositions. Theopacity, gloss, scratch resistance, and laydown of a printing ink can beimproved by incorporating the alkoxylated polymer into the printing ink.

DETAILED DESCRIPTION OF THE INVENTION

It is to be understood that the foregoing general description and thefollowing detailed description are exemplary and explanatory only, andare not restrictive of any subject matter claimed.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of skill in theart to which the inventions belong. All patents, patent applications,published applications and publications, websites and other publishedmaterials referred to throughout the entire disclosure herein, unlessnoted otherwise, are incorporated by reference in their entirety for anypurpose.

Definitions

In this application, the use of the singular includes the plural unlessspecifically stated otherwise. As used herein, the singular forms “a,”“an” and “the” are intended to include the plural forms as well, unlessthe context clearly indicates otherwise.

In this application, the use of “or” means “and/or” unless statedotherwise.

As used herein, the terms “comprises” and/or “comprising” specify thepresence of the stated features, integers, steps, operations, elements,and/or components, but do not preclude the presence or addition of oneor more other features, integers, steps, operations, elements,components, and/or groups thereof. Furthermore, to the extent that theterms “includes,” “having,” “has,” “with,” “composed,” “comprised” orvariants thereof are used in either the detailed description or theclaims, such terms are intended to be inclusive in a manner similar tothe term “comprising.”

As used herein, ranges and amounts can be expressed as “about” aparticular value or range. “About” is intended to also include the exactamount. Hence “about 5 percent” means “about 5 percent” and also “5percent.” “About” means within typical experimental error for theapplication or purpose intended.

As used herein, the term “backbone” of a polymer chain is a sequence ofpolymerized monomer units (“monomer residues”).

As used herein, a “pendant” group is a group that is attached to thebackbone of a polymer. The term pendant may be used to describe a groupthat is actually part of a polymerized monomer unit.

As used herein, a “terminal end” or “terminal group” is located at theend of the polymer chain and is chemically attached to a terminalmonomer unit. A terminal group may, for example, have a compositiondistinct from the composition of the backbone of the polymer. A“pendant” group may occur in a “terminal” position. As such, a“terminal” group is a special case of a “pendant” group.

As used herein, the term “laydown” or “lay” in the context of printingrefers to the smoothness and evenness of a printed ink or varnish. Poorlay or laydown means that the solid print areas of a printed ink orvarnish are not of a completely uniform film thickness.

As used herein, the terms “opacity” or “contrast ratio opacity” of apigmented ink or coating refers to its ability to cover the color orcolor differences of a substrate. Opacity depends on the amount of lightthat is transmitted through, or reflected from, the surface of the ink.More opaque colorants have a greater tendency to reflect and refractlight.

As used herein, the term “gloss” of an ink is a measure of its abilityto reflect incident light. It largely depends on whether or not the inkforms a smooth film on the surface of the substrate.

As used herein, the term “di- or higher” when referring to compoundswith functional groups means to a chemical compound with two or morefunctional groups with an active hydrogen. Such functional groupsinclude hydroxyl, carboxyl, thiol, amino, imino, amido, and ureido.

As used herein, “tri- or higher functional polyol” refers to a chemicalcompound with three or more functional hydroxyl groups. A polyol may bea polymer with three or more functional hydroxyl groups.

As used herein, the term “diol” refers to a chemical compound with twofunctional hydroxyl groups. A diol may be a polymer with two functionalhydroxyl groups.

As used herein, the term “additional functional groups,” when used inthe context of an alkoxylated polymer, refers to the presence ofdifferent functional groups on the polymer backbone, such as, forexample, COOH, in addition to the functional hydroxyl groups.

As used herein, “acid value” is the weight in milligrams of KOH requiredto neutralize the pendant carboxylate groups in one gram of polymer.

As used herein, “hydroxyl value” is a measure of the number of hydroxylgroups present in a polymer. It is expressed as the weight in mg of KOHrequired to neutralize the hydroxyl groups in one gram of polymer. It isdetermined by acetylation using acetic anhydride, and titration of theacetic acid and excess anhydride with KOH.

As used herein, “polydispersity” or “dispersity” is the measure of thebroadness of a molecular weight distribution of a polymer. It iscalculated as M_(w)/M_(n), wherein M_(w) is the weight average molecularweight of the polymer, and M_(n) is the number average molecular weightof the polymer. A polydispersity index ratio of 1 means that all thechain lengths are equal.

As used herein, “yield value,” is a feature of the non-Newtonianbehavior of inks, wherein a distinct shear stress or force is requiredbefore any deformation or flow takes place.

As used herein, “Tg” or “glass transition temperature” is thetemperature range where a thermosetting polymer changes from a hard,rigid or “glassy” state to a more pliable, compliant or “rubbery” state.

Alkoxylated Polymers

In a particular aspect, the present invention provides an alkoxylatedpolymer comprising:

-   -   a) a backbone with one or more alkoxylated sites;    -   b) terminal ends each of which is a site that can be        alkoxylated; and    -   c) one or more polyfunctional monomers or oligomers having two        or more functional polar groups with an active hydrogen, or        mixtures thereof.

The functional polar groups are preferably hydroxyl, carboxyl, thiol,amino, imino, amido, or ureido. Preferably, at least one of the monomersand/or oligomers comprises one or more functional hydroxyl groups, suchas trimethylol propane.

The alkoxylated polymer may be any polymer suitable for the intendeduse. Examples of alkoxylated polymers include, but are not limited to,polyester, polyurethane, polyacrylic, and polyamide. Preferably, thealkoxylated polymer is an alkoxylated polyester.

There is no restriction on the monomers and/or oligomers used, as longas they can be functionalized with one or more of the functional polargroups discussed herein. Examples of monomers and/or oligomers that canbe used include, but are not limited to, acrylic and methacrylicmonomers, styrenic monomers, vinyl monomers, acrylonitrile monomers,butadiene monomers, alkene or alkenylene monomers, allyl monomers, andthe like.

Polymers may include terminal functional groups which can bealkoxylated. There may also be functional groups along the backbone ofthe polymer, either as part of the polymer chain, or as pendant groups.Any site with a functional group can be alkoxylated according to thepresent invention. Preferably, at least one of the alkoxylated sites ison the backbone of the polymer chain.

The polymers can be alkoxylated using an etherification process. Theetherification process comprises reacting a monofunctional polyalkyleneoxide glycol with a hydroxyl functional polymer. An esterificationprocess can also be used, wherein a monofunctional polyalkylene oxideglycol is reacted with a carboxylic acid functional polymer. Themonofunctional polyalkylene used in these reactions is preferablymonofunctional polyethylene glycol or monofunctional polypropyleneglycol.

The alkoxylated polymers can also be synthesized by reactingpoly(oxypropylene), preferably having one terminal hydroxyl group, witha diacid or anhydride to obtain a carboxyl functional reaction product,and reacting the product therefrom with a hydroxyl functional basepolymer, and obtaining a product having ether groups at each hydroxylsite of the base polymer. Alternatively, an alkoxylated polymer could bemade by reacting a poly(oxypropylene) with a diepoxide to obtain anepoxy functional reaction product, which is then reacted with a hydroxylfunctional base polymer, to obtain a polymer having ester groups formedat each hydroxyl of the base polymer. Similarly, instead of thediacid/anhydride or diepoxide, the first step would react thepoly(oxypropylene) with a diisocyanate, to produce an isocyanatefunctional reaction product, which is then reacted with a hydroxylfunctional base polymer, to obtain a polymer with urethane functionalgroups at each hydroxyl of the base polymer.

Any suitable alkoxylation can be used. Suitable alkoxylations includeethoxylation, propoxylation, and butoxylation. Preferably, the polymersare propoxylated.

Suitable hydroxyl functional monomers and/or oligomers include any typeof monomers and/or oligomers having two or more functional hydroxylgroups. Hydroxyl functional monomers and/or oligomers may contain onlyhydroxyl functional groups, or other functional groups in addition tothe hydroxyl groups. Examples of hydroxyl functional monomers and/oroligomers include, but are not limited to trimethylol propane, ethyleneglycol, diethylene glycol, 1,4-butandiol, 1,3-propanediol, hexanediol,2-methyl-1,3-propanediol, neopentylglycol, trimethylolethane,pentaerythritol, glycerol, 1,2,4-benzenetriol, 1,3,5-benzenetriol,1,2,3-benzenetriol, and the like. Preferably, at least one of thepolyfunctional monomers and/or oligomers is trimethylol propane.

Suitable carboxyl functional monomers and/or oligomers include any typeof monomers and/or oligomers having two or more functional carboxylgroups. Carboxyl functional monomers and/or oligomers may contain onlycarboxyl functional groups, or other functional groups in addition tothe carboxyl groups. Examples of carboxyl functional monomers and/oroligomers include, but are not limited to, acrylic and methacrylic acid,itaconic acid, crotonic acid, maleic acid, succinic acid, malonic acid,diethyl malonic acid, monobutyl maleate, 1,3-acetonedicarboxylic acid,azelaic acid, benzylmalonic acid, biphenyl-4,4′-dicarboxylic acid,1,3,5-cyclohexanetricarboxylic acid, cyclohexylsuccinic acid, and thelike.

Suitable thiol functional monomers and/or oligomers include any type ofmonomers and/or oligomers having two or more functional thiol groups.Thiol functional monomers and/or oligomers may contain only thiolfunctional groups, or other functional groups in addition to the thiolgroups. Examples of thiol functional monomers and/or oligomers include,but are not limited to, trimethylolpropane tris(3-mercaptopropionate);trimethylolpropane tris(2-mercaptoacetate); pentaerythritoltetrakis(2-mercaptoacetate); pentaerythritoltetrakis(3-mercaptopropionate); 2,2′-(ethylenedioxy)diethanethiol;1,3-propanedithiol; 1,2-ethanedithiol; 1,4-butanedithiol;tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate; and3,4-ethylenedioxythiophene, and the like.

Suitable amino functional monomers and/or oligomers include monomersand/or oligomers having two or more functional amino groups. Aminofunctional monomers and/or oligomers may contain only amino functionalgroups, or other functional groups in addition to the amino groups.Examples of amino functional monomers and/or oligomers include, but arenot limited to, m-phenylenediamine, p-phenylenediamine,1,3,5-triaminobenzene, 1,3,4-triaminobenzene, 3,5-diaminobenzoic acid,2,4-diaminotoluene, 2,4-diaminoanisole, and xylylenediamine,ethylenediamine, propylenediamine, and tris (2-diaminoethyl) amine, andthe like.

Suitable imino functional monomers and/or oligomers include monomersand/or oligomers that have two or more functional imino groups. Iminofunctional monomers and/or oligomers may contain only imino functionalgroups, or other functional groups in addition to the imino groups.Examples of imino functional monomers and/or oligomers include, but arenot limited to, bis(imino)pyridine; 3,3′-iminodipropionitrile;[2,6-bis(1-phenylimino)ethyl]pyridine, and the like.

Suitable amido functional monomers and/or oligomers include monomersand/or oligomers that have two or more functional amido groups. Amidofunctional monomers and/or oligomers may contain only amido functionalgroups, or other functional groups in addition to the amido group.Examples of amido functional monomers include, but are not limited to,norbomene diamide, 1,6-diazacyclododecane-2,5-dione, and the like.

Suitable ureido functional monomers and/or oligomers include monomersand/or oligomers that have two or more ureido functional groups. Ureidofunctional monomers and/or oligomers may contain only ureido functionalgroups, other functional groups in addition to the ureido functionalgroups. Examples of ureido functional monomers include, but are notlimited to, dimethylbis(ureido)silane, ureidopyrimidinone, and the like.

Advantageously, the alkoxylated polymers may be functionalized by one ormore diacids or anhydrides, or mixtures thereof. Suitable diacidsinclude, but are not limited to, adipic acid, phthalic acid,terephthalic acid, maleic acid, isophthalic acid, dimethyl isophthalate,1,4-cyclohexanediarbocylic acid, dimethyl terephthalate, sebacic acid,azelaic acid, and the like. Suitable anhydrides include, but are notlimited to, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,phthalic anhydride, trimellitic anhydride, maleic anhydride, succinicanhydride, and the like. Preferably, the anhydride is tetrahydrophthalicanhydride.

Advantageously, the alkoxylated polymers may be functionalized by one ormore COOH functional diols. Examples of COOH functional diols include,but are not limited to, dimethylolpropionic acid, dimethylolbutanoicacid, and the like. Preferably, the COOH functional diol isdimethylolpropionic acid.

The present invention is drawn to alkoxylated polymers. The alkoxylatedpolymers can be used for any purpose wherein polymers are used. Suchuses include, but are not limited to, ink and coating compositions,packaging such as bags and bottles, electrical applications such asinsulators or conductors on circuit boards, adhesives, protective films,flexible foams, road surfacing, etc. For example, the alkoxylatedpolymers can be used in printing inks and coatings to improve theopacity, gloss, scratch resistance, and laydown of the printing inks andcoatings. Preferably, such printing inks and coatings are high speedprinting inks and coatings. Thus, the present invention is also drawn toprinting inks and coatings comprising the alkoxylated polymers.

In a preferred example, the alkoxylated polymers are useful as additivesin ink and coating compositions. The polymers are useful as dispersants,and as low tack binders, in inks and coatings. When used as printing inkadditives, the alkoxylated polymers enable one skilled in the art toformulate printing inks having various improved properties. In the caseof colored flexographic and colored gravure printing inks, the printinginks comprising the alkoxylated polymers exhibit higher opacity at aviscosity which is comparable to commercially available printing inks.Alternatively, the printing inks of the invention have lower viscositythan commercially available printing inks at equal opacity. In the caseof printing inks that contain colorants other than white (or incombination with white colorants), the printing inks of the presentinvention exhibit lower viscosity and improved laydown versus printinginks that do not contain the alkoxylated polymers of the presentinvention.

The alkoxylated polymers of the present invention may be used as adispersant or low tack binder in all types of printing ink formulations,including but not limited to solvent-based, water-based andenergy-curable printing ink formulations. Preferably, the printing inksare flexographic or gravure printing ink formulations. Preferably, theprinting inks or coatings are energy curable.

Occasionally, one or more polymers, or resins, in an ink or coatingcomposition do not work well together. In a preferred example, thealkoxylation of the polymer improves the compatibility of the polymerwith other polymers and resins in an ink or coating composition.

The alkoxylated polymers may be present in a printing ink or coating inan amount of from about 0.1 to 20 wt %; 0.1 to 15 wt %; 0.1 to 11 wt %;or 0.1 to 5 wt %. The alkoxylated polymers may be present in a printingink or coating in an amount of from about 0.5 to 15 wt %; 0.5 to 5.0 wt%; or 1.0 to 2.0 wt %.

Colorants suitable for use in the printing ink formulations of thepresent invention include, but are not limited to, organic or inorganicpigments and dyes. The dyes include, but are not limited to, azo dyes,anthraquinone dyes, xanthene dyes, azine dyes, combinations thereof andthe like. Organic pigments may be one pigment or a combination ofpigments, such as for instance Pigment Yellow Numbers 12, 13, 14, 17,74, 83, 114, 126, 127, 174, 188; Pigment Red Numbers 2, 22, 23, 48:1,48:2, 52, 52:1, 53, 57:1, 112, 122, 166, 170, 184, 202, 266, 269;Pigment Orange Numbers 5, 16, 34, 36; Pigment Blue Numbers 15, 15:3,15:4; Pigment Violet Numbers 3, 23, 27; and/or Pigment Green Number 7.Inorganic pigments may be one of the following non-limiting pigments:iron oxides, titanium dioxides, chromium oxides, ferric ammoniumferrocyanides, ferric oxide blacks, Pigment Black Number 7 and/orPigment White Numbers 6 and 7. Other organic and inorganic pigments anddyes can also be employed, as well as combinations that achieve thecolors desired.

As with most printing ink formulations or compositions, additives may beincorporated to enhance various printing and printability properties ofthe printing ink. A partial list of such additives include, but is notlimited to, adhesion promoters, light stabilizers, de-gassing additives,flow promoters, defoamers, antioxidants, UV stabilizers, surfactants,dispersants, plasticizers, rheological additives, waxes, silicones, etc.

Synthesis of Alkoxylated Polymers

Alkoxylated polymers can be prepared in several ways. The followingsynthetic schemes are representative of processes that can be used. Itis to be understood that these are exemplary only, and one of skill inthe art may use other processes, which would also fall within the scopeof the invention.

General Scheme for Alkoxylation of Hydroxyl Functional Polymers byPolymerization of an Alkylene Oxide

One process for preparing alkoxylated polymers involves thepolymerization of an alkylene oxide. The polymerization initiator istypically an alcohol and the catalyst employed in the reaction is a base(typically alkali metal or alkali earth hydroxide or cyanide). When theinitiator is, for example, propylene glycol or water, the resultingpolymer is linear. The alkoxylation reaction is typically run underpressure (for example 3 to 7 bar) and at an elevated temperature (forexample 100° C. to 160° C.). The synthesis below illustrates a processwherein the alkylene oxide is propylene oxide.

General Scheme for Alkoxylation of Hydroxyl Functional Polymers Using aPolymerization Initiator

Another process for preparing alkoxylated polymers includes the use of apolymerization “initiator,” such as, for example, any hydroxylfunctional polyester. The resulting alkoxylated polymer will be slightlybranched. The scheme shown below is a generalized alkoxylation reactionscheme, illustrating the use of propylene oxide as the alkylene oxide.The resulting trifunctional structure could be a “base” hydroxylfunctional polyester as described below.

Once all of the primary hydroxyls have reacted with propylene oxide, thesecondary hydroxyls, formed during the initial propoxylation, will beginto react with propylene oxide. This reaction will continue on all of thesecondary hydroxyls until all of the propylene oxide has reactedresulting in polypropylene oxide (PO) units at each of the originalprimary hydroxyl sites. The number of PO units can be regulated throughinitial PO charge, catalyst, temperature and pressure.

It will be understood by one skilled in the art that the processingconditions are for exemplary purposes and that the processing stepsand/or materials could be modified and still fall within the scope ofthe present invention. It is also well understood and readily acceptedby one skilled in the art that the exemplary polyester described inScheme 2 may comprise additional functional groups, e.g. carboxylicmoieties, which may also participate in alkoxylation and that otheralkylene oxides may be substituted for the propylene oxide. Suitableoxide substitutes include, but are not limited to, butylene oxide,ethylene oxide, styrene oxide and diepoxides like bisphenol A diglycidylether. Finally, it will be further understood by one skilled in the artthat other hydroxyfunctional polymers comprising hydroxyl and/orcarboxylic acid functionality may be substituted for the polyester, e.g.acrylic or epoxy polymers.

Alkoxylation of Hydroxyl Functional Polyester-Polyether Block Copolymers

U.S. Pat. No. 6,753,402 B1 (Example 4) teaches the preparation of apolyester-polyether block copolymer. In a 250 ml stirring autoclave, 2.0g of the DMC (double metal cyanide) catalyst as described in Example 3of the patent is dispersed in 130 g of polyesterol A at 110° C. Thesubsequently acquired suspension is then evacuated at 3 mbar for 2hours. The reaction mixture is subsequently made inert by means of 10bar nitrogen pressure. At an autoclave pressure of 0.5 bar of nitrogenand a temperature of 130° C., 70 g of propylene oxide is then added overa period of 5 minutes using a nitrogen admission pressure of 10 bar.After 2 hours, the reaction mixture is degassed at a reduced pressure of5 mbar and a temperature of 100° C. One skilled in the art would beaware that one could substitute KOH or another alkali metal or alkalineearth hydroxide or oxide for the DMC catalyst and could substitute thehydroxyl functional polymer with the polyesterol.

U.S. Pat. No. 6,753,402 B1 (Example 5) teaches the preparation of apolyester-polyether block copolymer. In a 250 ml stirring autoclave, 1.0g of the DMC catalyst as described in Example 3 of the patent isdispersed in 130 g of polyesterol B at 110° C. The subsequently acquiredsuspension is then evacuated at 3 mbar for 2 hours. The reaction mixtureis subsequently made inert by means of 10 bar nitrogen pressure. 70 g ofpropylene oxide is then added at 130° C. After 3 hours, the reactionmixture is degassed at a reduced pressure of 4 mbar and a temperature of90° C. One skilled in the art would be aware that one could substituteKOH or another alkali metal or alkaline earth hydroxide or oxide for theDMC catalyst and could substitute the hydroxyl functional polymer withthe polyesterol.

Preparation of Polyoxyalkylene Diols

U.S. Pat. No. 2,425,845 teaches the preparation of mixtures ofpolyoxyalkylene diols and methods of making such mixtures (Example 1 ofthe patent). A polyoxyalkylene glycol starting material of relativelylow molecular weight is prepared. The moisture content of the diethyleneglycol is about 0.15 percent and of the mixed oxides, about 0.07percent. The reaction mixture is vigorously agitated and maintained at atemperature of about 119° C. to 127° C. throughout the reaction. About15 minutes into the reaction, the oxides are supplied to the reactionmixture at a rate to maintain a pressure of about 16 psi. After theoxides are added, the reaction mixture is recycled for a period of 30minutes. A part of the reaction product is neutralized to a pH of 7 to8, with concentrated sulfuric acid, and filtered. The reactor product isa liquid found to have a viscosity of 26.8 centistokes (127 SayboltUniversal seconds) at 100° F., and an average molecular weight of about227 (as determined by its acetyl value).

A mixture of 60 parts of ethylene oxide and 20 parts of 1,2-propyleneoxide is introduced into a reactor containing 20 parts of theunneutralized reactor product resulting from the above procedure at arate to maintain a pressure of about 22 to 30 psi over a period of about1 hour. No additional sodium hydroxide is added and the moisture contentof the oxides is the same as above. A temperature of about 111° C. to122° C. is maintained during the reaction and the reaction mixture isrecycled for about one-half hour after all the oxides are introduced.The product is a liquid which is found to contain about 0.25 percent ofwater and to have an alkalinity (calculated as sodium hydroxide) ofabout 0.78 percent.

A part of the reaction product is then neutralized with concentratedsulfuric acid and filtered. The resulting product is a liquid having aviscosity of 112.6 centistoke (520 S. U. S.) at 100° F. and an averagemolecular weight of about 1,060 (as determined by acetylation). Thisdiol composition is found also to be miscible in all proportions withcold water. One skilled in the art would be aware that one couldsubstitute hydroxyl functional polymers for the unneutralizedpolyoxyalkylene glycol synthesized in the procedure.

Butoxylation of Hydroxyl Functional Polymer

-   U.S. Pat. No. 5,145,948 A (Example 1) teaches an alkali    polymerization catalysts reaction where two adducts of 1,2-butylene    oxide with alcohols are prepared. A dehydrated mixture of the    alcohol used as the initiator and KOH is initially taken in a    pressure vessel, the amount of KOH used being about 0.01 to 1,    preferably 0.05 to 0.5, e.g. 0.1, % by weight of the expected total    weight of the reaction product. The vessel is then flushed several    times with nitrogen and heated to 140° C. to 150° C., after which    the 1,2-butylene oxide is fed continuously or batch wise in the    reaction mixture with stirring, at constant temperature and under    from 5 to 30 bar, via a dip tube or onto the surface, until the    desired viscosity is reached. The volatile constituents are removed,    advantageously under reduced pressure, and, if necessary, the    product is clarified by filtration. One skilled in the art would be    aware that one could substitute hydroxyl functional polymers for the    dehydrated mixture of the alcohol.

Alkoxylation of Hydroxyl Functional Polymers Using Poly(Oxypropylene)and Anhydride

Polymers may be produced, without using epoxides, from LB fluids. LBFluids (manufactured by Dow Chemical) are alcohol-started base stocksfeaturing oxypropylene groups with one terminal hydroxyl group. They areavailable in variety of molecular weights varying by the amount of PO.

Procedure (Step 1)

Esterify a selected LB fluid with enough anhydride as required (e.g.tetrahydrophthalic anhydride) so that all of the hydroxyls on the LBfluid are end capped with the anhydride leaving a carboxyl group at theend of each LB fluid.

One skilled in the art would be aware that the acid functional polymerof Step 1 could be omitted and proceed directly to Step 2.

Procedure (Step 2)

The carboxyl functional reaction product from step 1 is then reactedwith a hydroxyl functional polyester (or polyurethane or acrylic) at anequimolar ratio forming ester groups at each hydroxyl site on the “base”polymer. The resulting polymer would be almost identical to apropoxylated hydroxyl functional polymer except for the ester linkagesand the fact that the polymer would not have a hydroxyl value. Thepropoxylated polymer will have secondary hydroxyl functionality at theend of the propoxylation chain providing the final polymer with ahydroxyl value. It will be appreciated by one skilled in the art that amonofunctional polyethylene glycol could be substituted for the LBfluid, to yield a similar propoxylated material.

Synthesis of Branched Low-Tg Polyesters with Endcappers

Long chain branched polyesters are synthesized using monofunctionalendcappers such as 1-dodecanol and poly(propylene glycol) monobutylether to avoid gelation at high conversions. Poly(propylene glycol)monobutyl ether 1-dodecanol endcapped polyesters are synthesizedfollowing a similar procedure as explained above. Branching reagent(trimethyl benzene-1,3,5-tricarboxylate, 2 mol %), is pre-reacted withdiethylene glycol at 180° C. for 30 min and subsequently a diestermonomer (dimethyl cyclohexane-1,4-dicarboxylate) is added. The reactionproceeds under nitrogen atmosphere at 200° C. for 4 h and the endcappersare added and the temperature set to 220° C. over 30 min. Vacuum isapplied gradually and the temperature is then set to 250° C. for 2hours. Aliquots of the reaction mixture are removed from the reactionmixture and analyzed using size exclusion chromatography (SEC). Thesolubility of the samples are tested in chloroform and the reaction isstopped prior to the gel point of the reaction mixture.

Alkoxylation of Hydroxyl Functional Polymers Using Poly(Oxypropylene)and Epoxides

Polymers are produced by reacting epoxides with LB fluids. LB Fluids(manufactured by Dow Chemical) are alcohol-started base stocks featuringoxypropylene groups with one terminal hydroxyl group. They are availablein variety of molecular weights varying by the amount of PO.

Procedure (Step 1)

Selected LB fluid is reacted with enough diepoxide (for example,resorcinol glycidyl ether) so that all of the hydroxyls on the LB fluidare end capped with the diepoxide leaving an epoxy group at the end ofeach LB fluid.

Procedure (Step 2)

The epoxy functional reaction product from Step 1 is then reacted with ahydroxyl functional polyester (or polyurethane or acrylic) at anequimolar ratio forming ether groups at each hydroxyl site on the “base”polymer. The resulting polymer is almost identical to the propoxylatedpolymers except for the fact that the resulting polymer will not have ahydroxyl value. The propoxylated polymer will have secondary hydroxylfunctionality at the end of the propoxylation chain providing the finalpolymer with a hydroxyl value. It will be understood by one skilled inthe art that a monofunctional polyethylene glycol could be substitutedfor the LB fluid, to yield a similar material and that ether linkage maybe formed starting with a hydroxyl functional polymer, e.g. a hydroxyfunctional polyester. It will be understood by one skilled in the artthat a hydroxy functional alkylene oxide could be substituted with acidcatalysts to furnish an alkoxylated polymer, e.g. an alkoxylatedpolyester.

Alkoxylation of Hydroxyl Functional Polymers Using Poly(Oxypropylene)and Diisocyanate

Polymers may be produced, without using epoxides, from LB fluids. LBFluids (manufactured by Dow Chemical) are alcohol-started base stocksfeaturing oxypropylene groups with one terminal hydroxyl group. They areavailable in variety of molecular weights varying by the amount of PO.

Procedure (Step 1)

React a selected LB fluid with enough diisocyanate as required (e.g.isophoronediisocyanate) so that all of the hydroxyls on the LB fluid areend capped with the diisocyanate leaving an isocyanate group at the endof each LB fluid.

Procedure (Step 2)

The isocyanate functional reaction product from step 1 is then reactedwith a hydroxyl functional polyurethane (or polyester or acrylic) at anequimolar ratio forming urethane groups at each hydroxyl site on the“base” polymer. The resulting polymer would be almost identical to apropoxylated hydroxyl functional polymer except for the urethanelinkages and the fact that the polymer would not have a hydroxyl value.The propoxylated polymer will have secondary hydroxyl functionality atthe end of the propoxylation chain providing the final polymer with ahydroxyl value. It will be appreciated by one skilled in the art that amonofunctional polyethylene glycol could be substituted for the LBfluid, to yield a similar propoxylated material.

EXAMPLES

The following examples illustrate specific aspects of the presentinvention and are not intended to limit the scope thereof in any respectand should not be so construed.

Synthesis of Alkolylated Polymers

Examples 1 to 10 describe the synthesis of alkoxylated polymers.

Example 1

An alkoxylated hydroxyl functional polyester was synthesized accordingto the formulation in Table 1.

TABLE 1 Alkoxylated hydroxyl functional polyester Material Amount (%) ATrimethylol propane 36.5 B 1,4-butanediol 17.5 C Tetrahydrophthalicanhydride 52.4 D Water-decanted from −6.4 condensation polymerizationTotal 100.0

To a thoroughly cleaned and purged reactor, components (A), (B), and (C)were added. The reactor was then purged with nitrogen and thetemperature brought to about 170° C. over 1 hour. The temperature of thereactor was slowly brought to 217° C., and the condenser temperature wasnot allowed to exceed 100° C. Water formed as a result of thepolymerization reaction was removed via a decanter. The reaction wascontinued at 217° C. until the acid value was below 7. Once the acidvalue was below 7, the reaction mixture was filtered and discharged, andcooled to 135° C., and the alkoxylation reaction (more specifically herepropoxylation) was begun.

Example 2

An alkoxylated hydroxyl and carboxyl functional polyester wassynthesized according to the formulation in Table 2.

TABLE 2 Alkoxylated hydroxyl and carboxyl functional polyester MaterialAmount (%) A Trimethylol propane 33.7 B Dimethylolpropionic acid 24.1 CTetrahydrophthalic anhydride 48.2 D Water-decanted from −6.0condensation polymerization Total 100.0

To a thoroughly cleaned and purged reactor, components (A), (B), and (C)were added. The reactor was then purged with nitrogen and thetemperature brought to about 170° C. over 1 hour. The temperature of thereactor was slowly brought to 183° C. until the acid value of thereaction mixture was 85. Once the acid value was 85, the reactionmixture was filtered and discharged, and cooled to 135° C., and thepropoxylation reaction begun.

Although the alkoxylated hydroxyl functional polyesters in Examples 1and 2 were synthesized “neat” (without solvents), the polyester couldalso be synthesized in the presence of one or more solvents. Examples ofsuitable solvents that could be used in the synthesis include, but arenot limited to, petroleum solvents (e.g. heptane); alcohols (e.g. propylalcohol, isopropyl alcohol, butyl carbitol, propasol p(1-propoxy-2-propanol), diacetone alcohol, etc.); esters (e.g. ethylacetate, propyl acetate, pm acetate (1-methoxy-2-propyl-acetate),isopropyl acetate), and the like.

Additionally, other materials could be used instead of, or in additionto, the materials A, B, and C recited in Examples 1 and 2. Examples ofsuch materials include, but are not limited to, the following:

-   -   Material A: trifunctional (and above) polyols such as        trimethylolethane, pentaerythritol, glycerol,        1,2,4-benzenetriol, 1,3,5-benzenetriol, 1,2,3-benzenetriol.    -   Material B: —COOH functional diols, such as dimethylolbutanoic        acid.    -   Material B: other low MW short-chain diols could also be used,        such as ethylene glycol, 1,4 butandiol, 1,3 propane diol,        pentanediol, hexanediol, 2-methyl-1,3-propanediol,        neopentylglycol.    -   Material C: Diacids and/or anhydrides such as hexahydrophthalic        anhydride, phthalic anhydride, isophthalic acid, trimellitic        anhydride, maleic anhydride, succinnic anydride, dimethyl        isophthalate, 1,4-cyclohexanedicarboxylic acid, dimethyl        terephthalate, adipic acid, sebacic acid, azelaic acid.

Example 3

An alkoxylated hydroxyl functional polyester was synthesized accordingto the formulation of 3a in Table 3 (Step 1) and formulation 3b in Table4 (Step 2).

TABLE 3 Synthesis of Example 3a (Step 1) Material Amount (%) A UCONLB-65 69.1 B Tetrahydrophthalic anhydride 30.9 Total 100.0

To a thoroughly cleaned and purged reactor, components (A) and (B) wereadded. The reactor was then purged with nitrogen and the temperaturebrought to 187° C. until an acid value of 115 was reached. The polymerwas poured out hot (solids=100%; viscosity=1,200 cps).

TABLE 4 Synthesis of Example 3b (Step 2) Material Amount (%) AOH—functional polyester 28.9 of Example 1 B 3a 71.1 Total 100.0

To a thoroughly cleaned and purged reactor, components (A) and (B) wereadded. The reactor was then purged with nitrogen and the temperaturebrought to 220° C. The polymer gels.

Example 4

Example 4 was synthesized in the same manner as Example 3, except thatthe tetrahydrophthalic anhydride in Step 1 was replaced with isophoronediisocyanate. An alkoxylated hydroxyl functional polyester wassynthesized according to the formulation of 4a in Table 5 (Step 1) andformulation 4b in Table 6 (Step 2).

TABLE 5 Synthesis of Example 4a (Step 1) Material Amount (%) A UCONLB-65 60.5 B Isophorone diisocyanate 39.5 Total 100.0

To a thoroughly cleaned and purged reactor, components (A) and (B) wereadded. The reactor was then purged with nitrogen and the temperaturebrought to 65° C. until % NCO=7.5% was reached. The polymer was pouredout hot (solids=100%; viscosity=700 cps).

TABLE 6 Synthesis of Example 4b (Step 2) Material Amount (%) AOH—functional polyester 26.9 of Example 1 B 4a 73.1 Total 100.0

To a thoroughly cleaned and purged reactor, components (A) and (B) wereadded. The reactor was then purged with nitrogen and the temperaturebrought to 90° C. until % NCO<0.05%. The solid was dissolved in an 80/20blend of n-propanol/n-propyl acetate at 60% solids. Viscosity was 440cps.

Example 5

An alkoxylated polymer can be made according to the following procedure.635 g of a polyester of ethylene glycol and adipic acid (OH-number 177)(1 mol) and 700 g of polypropylene 3 ether glycol (OH-number 160) (1mol) are introduced into a flask fitted with a descending condenser. Thereaction mixture is first dehydrated with stirring at temperature of130° C., and a pressure of 12 mmHg. Then, 0.035 ml of concentratedsulphuric acid is introduced into the anhydrous melt at about 100° C.under a current of nitrogen. The temperature is then gradually raised to220° C., when the elimination of water due to etherification sets in.After 9 hours at 220° C. and 0.4 mmHg, the OH number is found to beabout 84, and the acid number about 0.17. After a further 8 hourscondensation at 220° C. and 0.4 mmHg, the OH-number is about 57.8 andthe acid number is about 0.4. The total amount of distillate obtained isabout 23 g. The sulphuric acid in the condensation product isneutralized by adding 0.3 g of barium carbonate with stirring, and theproduct is left to cool. The waxy condensation product has a softeningpoint of 28° C. Expected Yield: 1300 g.

Example 6

Propoxylated polyesters were made as described in Examples 6a and 6b.

Example 6a

A 250 ml flask was filled with 0.0124 moles (71.9 g) of a poly(ethyleneglycol-polypropylene glycol-polyethylene glycol) tri-block copolymer(5800 daltons, Sigma-Aldrich), 0.319 moles (33.2 g) of neopentyl glycol(Sigma-Aldrich) and 0.329 moles (48.7 g) of phthalic anhydride(Sigma-Aldrich). It was blanketed with nitrogen and heated to 90° C.Mechanical stirring was started and the temperature increased to 130° C.Then, 0.002 moles, (0.40 g) para-toluene sulfonic acid monohydrate(Sigma-Aldrich) was added. The reaction was heated to 160° C. for 3hours, and then to 190° C. for 4 hours. Water was removed from thesystem via a dean-stark trap. The reaction was stopped and the clearresin was poured into a lined metal can. M_(w) via GPC was 7500 Dalton,polydispersity 1.24.

Example 6b

A 250 ml flask was filled with 0.0124 moles (71.9 g) of a poly(ethyleneglycol-polypropylene glycol-polyethylene glycol) tri-block copolymer(5800 daltons, Sigma-Aldrich), 0.319 moles (33.9 g) of diethylene glycol(Sigma-Aldrich) and 0.312 moles (46.2 g) of phthalic anhydride(Sigma-Aldrich). It was blanketed with nitrogen and heated to 140° C.Mechanical stirring was started and 0.002 moles, (0.40 g) para-toluenesulfonic acid monohydrate (Sigma-Aldrich) was added. The temperature wasincreased to 180° C. for 7 hours. Water was removed from the system viaa dean-stark trap. The reaction was stopped and the clearreddish-colored resin was poured into a lined metal can. M_(w) via GPCwas 3600 Dalton with a polydispersity of 4.8.

Example 7

A hydroxyl functional polyurethane is synthesized according to theformulation in Table 7.

TABLE 7 Alkoxylated polyurethane Material Amount (%) A n-Propyl acetate40.0 B Trimethylol propane 18.29 C 1,4-butanediol 8.47 D K-KAT 3480.0046 E Isophoronediisocyanate 33.2354 Total 100.0

To a thoroughly cleaned and purged reactor, components (A), (B), (C) and(D) were added. When (B) was dissolved, (E) was added over 30 minutes.The reactor temperature was then brought to 85° C. over 2 hours.

To alkoxylate the polyurethane, you hold the reaction at a temperatureof 85° C. until % NCO<0.1%. Once the % NCO is below 0.1%, filter anddischarge the product, or vacuum strip off the n-propyl acetate, bringreaction temperature to 135° C. and begin alkoxylation (morespecifically propoxylation).

Example 8

An alkoxylated polyurethane was synthesized according to the formulationin Tables 8 and 9.

TABLE 8 Synthesis of 8a (Step 1) Material Amount (%) A UCON LB-65 60.496B Isophorone diisocyanate 39.5 C K-KAT 348 (catalyst) 0.004 Total 100.0

To a thoroughly cleaned and purged reactor, components (B) and (C) wereadded. The reactor was then purged with nitrogen and the temperaturebrought to 65° C. at which time (A) was added over 6 hours whilemaintaining a reaction temperature below 68° C. Once all of (A) wasadded, the temperature was held at 65° C. until % NCO=7.5% was reached.The polymer was poured out hot (solids=100%; viscosity=700 cps).

TABLE 9 Synthesis of 8b (Step 2) Material Amount (%) A OH—functionalpolyurethane 25.2* of Example 7 B 8a 44.9* C n-Propanol 29.9 Total 100.0*The amount of A & B must be calculated (hydroxyl and NCO equivalentsshould be equal) each time based on their OH value (A) & % NCO (B)

To a thoroughly cleaned and purged reactor, component (A) was added. Thereactor was then purged with nitrogen and the temperature brought to 90°C. Item (B) was then added over 20 minutes. Once all of (B) had beenadded, the temperature was held at 90° C. until % NCO=<0.05%. Then (C)was added, and the product cooled and discharged. The final polymer hada solids content of 60% and a viscosity of 1,090 cps.

Example 9

An alkoxylated alkoxylated hydroxyl/carboxyl functional polyacrylate issynthesized according to the formulation in Table 10.

TABLE 10 Alkoxylated hydroxyl/carboxyl functional polyacrylate MaterialAmount (%) A Ethyl acetate 45.0 B Methyl Methacrylate 15.97 C ButylMethacrylate 11.71 D 2-Ethylhexyl Acrylate 4.68 E Hydroxypropyl Acrylate6.09 F Methacrylic Acid 10.3 G Vazo 52 (CAS # 4419-11-8) 1.25 H Ethylacetate 5.0 Total 100.0

-   -   1. Add (A) to a clean reactor with slow nitrogen blanket. Set        reactor overhead for reflux conditions. Start mixing and heat to        77° C. to reflux.    -   2. Add (G-H) and (B-F) simultaneously (separate feeds) over 3        hours while maintaining reflux (reaction temperature of 77-78°        C.).    -   3. Once these additions are complete, hold for 3 hours and        increase reaction temperature to 77-79° C.    -   4. Vacuum strip/distill off the ethyl acetate. The resulting        polyacrylate will have a hydroxyl value of 55 and an acid value        of 138. Once all ethyl acetate is removed, increase reaction        temperature to 135° C. and begin alkoxylation reaction (more        specifically propoxylation).

Example 10

An alkoxylated carboxyl functional polystyrene/acrylic is synthesized byalkoxylating (more specifically propoxylating) a solid carboxylfunctional commercial styrene/acrylate (for example Joncryl 682 orJoncryl 678, both manufactured by BASF).

Printing Inks Comprising the Alkoxylated Polymers

Examples 11 to 23 describe the preparation and testing of printing inks.The properties of the printing inks were tested using the followingmethods:

-   -   Viscosity: Viscosity was measured using a Viscolite 700        viscometer from Hydramotion Co.    -   Opacity: Opacity was measured using a BNL-3 Opacimeter by        Technidyne, set on opacity readings.    -   Adhesion: Adhesion was measured by the 610 scotch tape test        according to ASTM F2252-03.    -   Gloss: Gloss was measured using a BYK-Micro Tri Gloss at an        angle of 60 degrees.    -   Scratch Resistance: Scratch resistance was measured by        scratching the printed ink or coating with the back of a        fingernail (10 scratches).    -   Wear: Wear was measured with the Sutherland Rub Tester using 100        rubs with a 4 pound test strip.    -   Laydown: Laydown was assessed by optical microscopy using bright        field illumination.    -   Particle Size: Particle size was measured by laser diffraction.

Example 11

Two white inks were assembled, one using the alkoxylated polymer fromExample 4 (Example 11a in Tables 11 and 12), the other the alkoxylatedpolyester of Example 1 (Example 11 b in Tables 11 and 12). The inks wereformulated with equal percent solids of dispersant. The inks wereprepared according to the formulations in Table 7.

TABLE 11 Formulation of flexographic white printing inks Example 11aExample 11b Unirez 2221 6.6 6.6 Example 1 / 0.23 Example 4b (70%) 0.32 /TR52 (TiO₂) 28.92 28.92 Akawax (erucamide) 0.7 0.7 Normal propanol 9.529.59 N-propyl acetate 2.00 2.02 Propasol P 1.70 1.70 Tap water 0.25 0.25Total 100.0 100.0

The inks were printed using a Harper Phantom Proofer (flexographic) onbread bag polyethylene. Test results are shown in Table 12. Both inksshowed good contrast ratio opacity when printed at press viscosity withExample 11a having an opacity of 57.31, and 11b with an opacity of56.07. The viscosity (low) at equal pigment loading of the experimentalink was similar to the standard. The maximum tack value of the two inkswas similar. Print quality of both inks was also favorable.

TABLE 12 Test performance of flexographic white inks Example 11a Example11b Viscosity (cps) 112.3 102.0 Tack 9.1 8.4 Opacity 57.31 56.07Adhesion Good Good Wear (15 sec) Good Good Scratch (nail) Good Good

Example 12

A flexographic white printing ink was prepared according to theformulation in Table 13.

TABLE 13 Flexographic white printing ink Typical Material % Range An-propanol 21.4 5-50% B diacetone alcohol 4.0 0-20% C styreneallylalcohol resin SAA-100 2.4 0-10% D Example 1 Alkoxylated Hydroxyl10.6 2-30% Functional Polyester E Plasticizer 2.1 0-10% F dibutylsebacate 0.3 0-10% G Dowanol DPM (dipropylene glycol 3.0 0-20%monomethyl ether) H butyl acetate 1.5 0-20% I n propyl acetate 3.0 0-20%J TR52 TiO₂ 48.0 0-75% K adhesion promoter 2.5 0-10% L propasol p 1.20-20% Total 100.0

A print test was performed comparing the opacity of the Example 12 whiteprinting ink to two commercially available printing inks at a similarviscosity. The two commercially available printing inks were FlexomaxWhite (Sun Chemical) and a White (Seigwerk). The printing inks wereprinted on a polyethylene substrate with a K-coater using a number 2coating rod. Their viscosity was measured using a Viscolite 700Viscometer. The opacity of the printing inks was measured using a BNL-3Opacimeter. The results are shown in Table 14.

TABLE 14 Properties of flexographic white printing inks Flexomax WhiteSeigwerk White (Comparative) (Comparative) Example 12 Opacity 47.6 47.953.3 Viscosity 121 115 127

Table 14 shows that the Example 12 printing ink has higher opacity atsimilar viscosity than two commercially available printing inks. Inanother embodiment, the Example 12 printing ink could be reduced inviscosity such that it is lower in viscosity to the two commercialprinting inks while having equivalent opacity. In another embodiment,inks could be made using the Example 1 polyester to produce printinginks based on colorants other than a white colorant or TiO₂, and theprinting ink could have increased opacity and/or color strength vs.commercial (prior art) printing inks at equivalent viscosity, or can besupplied at lower viscosity and equal opacity and/or color strength. Inanother embodiment, the formulation could be supplied without colorantsat lower viscosity vs. commercial (prior art) formulations.

Examples 13 and 14

Flexographic white printing inks were prepared according to theformulations in Table 15 (Example 12) and Table 16 (Example 13).

TABLE 15 Example 12 flexographic white printing ink (comparative) AmountMaterial (%) n-propyl Solvent 25.2 alcohol tap water Solvent 0.5Propasol P Solvent 3.9 Unirez 2221 polyamide resin 18.5 TR 52 TiO₂ 51.5Finawax E erucamide wax 0.4 Total 100.0

TABLE 16 Example 13 flexographic white printing ink Amount Matertial (%)n-propyl alcohol Solvent 15 n-propyl acetate Solvent 3.8 Unirez 2221polyamide 14 resin Example 1 Alkoxylated Hydroxyl 0.5 FunctionalPolyester TR 52 TiO₂ 61.1 AKAWAX E erucamide 1.5 wax tap water solvent0.5 Propasol P solvent 3.6 Total 100.0

A print trial was performed on a Chestnut printing press (21″ Sig 2 on a360/5.0 anilox) onto polyethylene bread bag stock. The followingprinting ink properties were evaluated:

Adhesion (610 tape test);

Gloss (BYK Tri-Glossmeter 60 degree);

Scratch Resistance (10 rubs with back of fingernail);

Opacity (BNL-3 Opacimeter) and Laydown (visual assessment).

The test results are reported in Table 17.

TABLE 17 Properties of flexographic white printing inks Example 12Property (comparative) Example 13 Adhesion Pass Pass Gloss 60 64 ScratchPass Pass (improved) Resistance Opacity 52.5 55.4 Laydown Pass Pass(improved)

Table 17 shows that the addition of an alkoxylated polyester (in thiscase propoxylated polyester) to a white flexographic printing ink as adispersant, improves the opacity, gloss, scratch resistance and laydownof the printing ink versus a comparative printing ink which does notcontain a propoxylated polyester dispersant of the present invention.

Examples 15 and 16

Gravure white printing inks were prepared according to the formulationsin Table 18 (Example 15) and Table 19 (Example 16).

TABLE 18 Example 15 gravure white printing ink (comparative) IsopropylAcetate 14.50 Ethyl Alcohol 8.00 N-Propyl Acetate 8.00 Nitrocellulose28.75 Plasthall ESO (epoxidized 7.00 soybean oil) Kronos 2063 TiO₂ 22.80TR-50 TiO₂ 6.00 ASP-G90—clay extender 1.50 MP22XF Paraffin Wax 1.65Adhesion Promoter 1.80

TABLE 19 Example 16 gravure white printing ink Isopropyl Acetate 14.50Ethyl Alcohol 8.00 N-Propyl Acetate 8.00 Nitrocellulose 18.75 PlasthallESO (epoxidized 7.00 soybean oil) Example 1 Alkoxylated Hydroxyl 1.0Functional Polyester Kronos 2063 TiO₂ 31.80 TR-50 TiO₂ 6.00 ASP-G90—clayextender 1.50 MP22XF Paraffin Wax 1.65 Adhesion Promoter 1.80 Total100.0

Using the same test method as described in Examples 13/14, the opacityof the Example 15 printing ink was 45 and the viscosity was 60 cps. Theopacity of the Example 16 printing ink was 52 and the viscosity was 60cps. Examples 15 (Comparative) and 16 show that, using the propoxylatedpolyester, it is possible to formulate a printing ink with aconsiderably higher titanium dioxide level (and thus higher opacity) ata similar viscosity.

Examples 17 and 18

Solvent-based flexographic magenta printing inks were prepared accordingto the formulations in Table 20 (Example 17) and Table 21 (Example 18).

TABLE 20 Example 17 solvent-based flexographic magenta printing ink(Comparative) Material Amount (%) Slow Lithol Rubine base 50Polyurethane varnish 40 80/20 N-propanol/propyl acetate 10 Total 100

The printing ink of Example 17 (Comparative) was a highly thixotropicprinting ink, typically most magentas colored printing inks are, and hada yield value of 1500 dynes/cm (as measured on a TA Instruments AR1500rheometer at 250° C.).

TABLE 21 Example 18 solvent-based magenta printing ink Amount Material(%) Slow Lithol Rubine base 50 Polyurethane varnish 39 Example 1Alkoxylated Hydroxyl 1.0 Functional Polyester 80/20 N-propanol/propylacetate 10 Total 100

The printing ink of Example 18 exhibited a reduced yield value (down to400 dynes/cm. using the same test method as described in Example 13).This resulted in better laydown for the printing ink (assessedvisually).

Examples 17 and 18 show that the addition of an alkoxylated polyester(in this case propoxylated polyester) to a solvent based flexographicmagenta printing ink, reduces viscosity and improves laydown of theprinting ink.

Examples 19 and 20

UV flexographic white printing inks were prepared according to theformulations in Table 22 (Example 19) and Table 23 (Example 20).

TABLE 22 Example 19 UV flexographic white printing ink (Comparative)Amount Material (%) Ketone resin 36.0 HDODA—Hexane diol diacrylate 4.0GENORAD 16 Inhibitor 0.3 IGM TPO photoinitiator 4.0 TetrahydrofurfurylAcrylate monofunctional monomer 12.7 TI-PURER-706 TiO₂ 42.0 BYK-501dispersant 1.0 Total 100.0

Example 19 ink had a viscosity of 4600 centipoise using the test methoddescribed in Example 11.

TABLE 23 Example 20 UV flexographic white printing ink Amount Material(%) Ketone resin 35.0 HDODA—Hexane diol diacrylate 4.0 GENORAD 16Inhibitor 0.3 IGM TPO photoinitiator 4.0 Tetrahydrofurfuryl acrylatemonofunctional monomer 12.7 Example 1 alkoxylated hydroxyl functionalpolyester 1.0 TI-PURER-706 TiO₂ 42.0 BYK-501 dispersant 1.0 Total 100.0

Example 20 ink had a viscosity of 1150 centipoise. This resulted inbetter laydown for the ink (assessed visually using the printing methoddescribed in Example 12).

Examples 19 and 20 show that the addition of propoxylated polyester tothe printing ink formulation as a dispersant reduces viscosity andimproves laydown in a UV-curing flexographic white printing ink.

In the above examples, the alkoxylated polymer was incorporated directlyinto the formula during the preparation of the finished printing inkformulation. In an alternate embodiment, the alkoxylated polymer couldbe incorporated into a dispersion which is then later made into afinished printing ink. This is a common base/concentrate printing inkformulation practice used in preparing conventional printing inks wherea dispersion and letdown vehicle system are employed.

Example 21

These alkoxylated polymer samples from Examples 1 and 6 were used toevaluate the effectiveness of incorporating them as dispersants in atypical solvent based white flexographic printing ink. White inks weremade using a standard formulation and adding the polymeric dispersant ofExample 1, Example 6a or Example 6b propoxylated polyesters (Table 24).

TABLE 24 White inks Ex. 1 6a 6b Polyamide 13.65 13.65 13.65 Example 10.3 Example 6a 0.3 Example 6b 0.3 TiO₂ 56.1 56.1 56.1 Akawax (erucamide)0.4 0.4 0.4 Alcohol 24.2 24.2 24.2 Acetate 5.15 5.15 5.15 additive 0.20.2 0.2 TOTAL 100 100 100

Inks were coated onto clear polyethylene film using a Phantom proofer(Harper) 6.8 volume 200 line anilox. The films were air dried at 43° C.for 60 seconds. Each of the inks were tested for viscosity using aViscolite model 700 (Hydramotion) and for opacity with a BNL-3Opacimeter (Technidyne). Viscosity of the undiluted ink was measured.The amount of solvent (%) required to reduce the inks to printingviscosity (i.e. 60 cps) is indicated in Table 25. The inks were printedat 60 cps, and opacity of the dried inks measured. The results are shownin Table 25.

TABLE 25 Opacity of the white inks Ex. 1 6a 6b Viscosity Uncut (cps)165.5 233.7 224.8 Amount of solvent (%) required 15 16 16 to reduceviscosity to 60 cps Opacity 53.0 52.7 52.5

The viscosity of the inks using Example 6a and Example 6b as adispersant before dilution was higher than the ink using Example 1 asthe dispersant. The opacity of the printed inks was equal.

Example 22

The particle size of a white reference ink (SL-800 White) alone wascompared to the particle size of SL-800 with the addition of either ofExample 6a or 6b alkoxylated polyesters. Particle size measurements weremade at 25° C. on a Laser Light Scattering (LLS) instrument, model LB500 manufactured by Horiba, using SL-800 ink as the standard. Resultsare shown in Table 26.

TABLE 26 Median particle size of reference ink alone and with Examples6a and 6b added SL-800 with SL-800 with SL-800 2.0% 2.0% White ExampleExample alone 6a added 6b added Median particle 1460 1200 1111 size (nm)

Particle size comparison indicates a modest reduction in particle sizewith the addition of either of the two alkoxylated polyesters comparedto the particle size of the SL-800 white sample in the absence of eitherdispersant. Particle size was reduced from about 1450 nm to 1100-1200nm.

Example 23

A white flexographic ink was made using the formulation in Table 27.

TABLE 27 White flexographic ink Material Amount (%) Normal propylalcohol 3.9 Propoxylated polyurethane (Example 8) 16.1 Nitro cellulosevarnish 6.0 Polamide resin (UNIREZ 2248) 2.0 Titanium dioxide (TR52)55.0 Propasol p solvent 17.0 Total 100.0

The ingredients are in weight percentage. The resulting ink had aviscosity of 320 cps. When let down to press ready viscosity of 78 cpsand printed using a flexographic proofer on a polyethylene substrate,the print showed excellent adhesion and scratch resistance. The opacitywas 56.

The present invention has been described in detail, including thepreferred embodiments thereof. However, it will be appreciated thatthose skilled in the art, upon consideration of the present disclosure,may make modifications and/or improvements on this invention that fallwithin the scope and spirit of the invention.

1.-32. (canceled)
 33. An ink or coating composition comprising analkoxylated polymer, wherein the alkoxylated polymer comprises: a) abackbone with one or more alkoxylated sites; b) terminal ends each ofwhich is a site comprising a functional polar group with an activehydrogen; and c) one or more polyfunctional monomers and/or oligomershaving two or more functional polar groups with an active hydrogen ormixtures thereof; wherein the alkoxylated polymer is present in anamount of 0.1 wt % to 20 wt %.
 34. The ink or coating composition ofclaim 33, wherein the functional polar groups are each independentlyselected from the group consisting of hydroxyl, carboxyl, thiol, amino,imino, amido, or ureido.
 35. The ink or coating composition of claim 33,wherein the alkoxylated polymer comprises at least one hydroxyl group.36. The ink or coating composition of claim 33, where the polyfunctionalmonomers and/or oligomers are functionalized by one or more diols. 37.The ink or coating composition of claim 33, wherein the polyfunctionalmonomers and/or oligomers are functionalized by one or more COOHfunctional diols, or mixtures thereof.
 38. The ink or coatingcomposition of claim 37, wherein at least one COOH functional diol isdimethylolpropionic acid.
 39. The ink or coating composition of claim33, wherein the polyfunctional monomers and/or oligomers arefunctionalized by one or more diacids or anhydrides, or mixturesthereof.
 40. The ink or coating composition of claim 39, wherein atleast one anhydride is tetrahydrophthalic anhydride.
 41. The ink orcoating composition of claim 33, wherein the one or more polyfunctionalmonomers or oligomers is selected from the group consisting oftrimethylol propane, ethylene glycol, diethylene glycol, 1,4-butandiol,1,3-propanediol, hexanediol, 2-methyl-1,3-propanediol, neopentylglycol,trimethylolethane, pentaerythritol, glycerol, 1,2,4-benzenetriol,1,3,5-benzenetriol, 1,2,3-benzenetriol, acrylic and methacrylic acid,itaconic acid, crotonic acid, maleic acid, succinic acid, malonic acid,diethyl malonic acid, monobutyl maleate, 1,3-acetonedicarboxylic acid,azelaic acid, benzylmalonic acid, biphenyl-4,4′-dicarboxylic acid,1,3,5-cyclohexanetricarboxylic acid, cyclohexylsuccinic acid,trimethylolpropane tris(3-mercaptopropionate); trimethylolpropanetris(2-mercaptoacetate); pentaerythritol tetrakis(2-mercaptoacetate);pentaerythritol tetrakis(3-mercaptopropionate);2,2′-(ethylenedioxy)diethanethiol; 1,3-propanedithiol;1,2-ethanedithiol; 1,4-butanedithiol;tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate; and3,4-ethylenedioxythiophene, m-phenylenediamine, p-phenylenediamine,1,3,5-triaminobenzene, 1,3,4-triaminobenzene, 3,5-diaminobenzoic acid,2,4-diaminotoluene, 2,4-diaminoanisole, and xylylenediamine,ethylenediamine, propylenediamine, and tris (2-diaminoethyl) amine,bis(imino)pyridine; 3,3′-iminodipropionitrile;[2,6-bis(1-phenylimino)ethyl]pyridine, norbornene diamide,1,6-diazacyclododecane-2,5-dione, dimethylbis(ureido)silane, andureidopyrimidinone.
 42. The ink or coating composition of claim 33,wherein the alkoxylated polymer is selected from the group consisting ofpolyester, polyurethane, polyacrylic, and polyamide.
 43. The ink orcoating composition of claim 33, wherein the alkoxylated polymer is analkoxylated polyester comprising: a) a backbone with one or morealkoxylated sites; b) terminal ends each of which is a site comprising afunctional polar group with an active hydrogen; c) one or more di- orhigher functional polyols; and d) one or more diacids or anhydrides, ormixtures thereof.
 44. The ink or coating composition of claim 33,wherein the alkoxylated polymer is an alkoxylated polyurethanecomprising: a) a backbone with one or more alkoxylated sites; b)terminal ends each of which is a site comprising a functional polargroup with an active hydrogen; c) one or more diisocyanates; and d) oneor more di- or higher functional polyols.
 45. The ink or coatingcomposition of claim 33, wherein the alkoxylated polymer is analkoxylated polyacrylic comprising: a) a backbone with one or morealkoxylated sites; b) terminal ends each of which is a site comprising afunctional polar group with an active hydrogen; c) one or more hydroxylfunctional acrylic monomers, or carboxyl functional acrylic monomers, ormixtures thereof; d) one or more additional acrylic or styrenicmonomers; and e) one or more di- or higher functional polyols.
 46. Theink or coating composition of claim 33, wherein the alkoxylated polymeris derived from a propoxylation, ethoxylation, or butoxylation process.47. The ink or coating composition of claim 46, wherein the alkoxylatedpolymer is derived from a propoxylation process.
 48. The ink or coatingcomposition of claim 33, wherein the alkoxylated polymer is present inan amount of 0.1 wt % to 15 wt %.
 49. The ink or coating composition ofclaim 33, wherein the alkoxylated polymer is present in an amount of 0.1wt % to 11 wt %.
 50. The ink or coating composition of claim 33, whereinthe alkoxylated polymer is present in an amount of 0.1 wt % to 5 wt %.51. The ink or coating composition of claim 33, wherein the alkoxylatedpolymer is present in an amount of 0.1 wt % to 3 wt %.
 52. The ink orcoating composition of claim 33, wherein the alkoxylated polymer ispresent in an amount of 0.1 wt % to less than 3 wt %.
 53. The ink orcoating composition of claim 33, wherein the alkoxylated polymer ispresent in an amount of 0.5 wt % to 15 wt %.
 54. The ink or coatingcomposition of claim 33, wherein the alkoxylated polymer is present inan amount of 0.5 wt % to 5 wt %.
 55. The ink or coating composition ofclaim 33, wherein the alkoxylated polymer is present in an amount of 1wt % to 2 wt %.
 56. The ink or coating composition of claim 33, whereinthe ink or coating composition is energy curable.
 57. The ink or coatingcomposition of claim 33, which further comprises a colorant.
 58. The inkor coating composition of claim 57, which is a printing ink.
 59. Theprinting ink of claim 58, wherein the ink is a white ink.
 60. Theprinting ink of claim 58, wherein the ink is a flexographic or gravureprinting ink.
 61. The ink or coating composition of claim 33, whereinthe alkoxylated polymer functions as a dispersant or low-tack binder.62. The ink or coating composition of claim 33, having improved opacity,gloss, scratch resistance, and laydown of the ink or coatingcomposition.